Oxazoline water repellant composition



OXAZOLINE WATER REPELLANT COMPOSITION Domenick D. Gagliardi, East Greenwich, R.I., assignor to Commercial Solvents Corporation, New York, N.Y., a

corporation of Maryland No Drawing. Filed June 7, 1966, Ser. No. 555,713 U.S. Cl. 26028.5 8 Claims Int. Cl. C08f 51/00, 53/16 ABSTRACT OF THE DISCLOSURE A water repellant composition comprising a thermosetting resin binder and an oxazoline of the formula:

wherein R is a lower alkyl radical having from I to 3 carbon atoms, a hydroxy methyl radical, or the radical -CH OOCR R is an alkyl radical having from about 12 to about 22 carbon atoms, R is an alkyl radical having from 1 to about 23 carbon atoms, and X is H or =CH The present invention relates to a process for treating fibrous materials and to compositions for use in the process. In a particular aspect, the present invention relates to novel compositions for rendering fibrous materials, and particularly textile materials, water repellent, said compositions comprising a thermosetting resin binder and an oxazoline of the formula:

RG- |3Hz N wherein R is a lower alkyl radical having from 1 to 3 carbon atoms, a hydroxy methyl radical, or the radical CH OOCR R is an alkyl radical having from about 12 to about 22 carbon atoms, R is an alkyl radical having from 1 to about 23 carbon atoms, and X is H or CH In a further aspect, this invention relates to a process for rendering fibrous materials, and particularly textiles, wtaer-repellent by application thereto of a thermosetting binder and an oxazoline of the formula:

wherein R and R are defined as above.

Much work has been devoted to providing methods for rendering textile materials water-repellent and many hydrophobic compounds have been suggested for this use. It is especially desirable that the water-repellency be retained after repeated launderings and dry cleanings. Such durable, water-repellent textiles are diflicult to obtain. In fact, many hydrophobic compounds used in rendering textiles water-repellent impart only a temporary Waterrepellent finish on the textile.

nited States Patent 0 It is an object of the present invention to provide novel compositions for imparting durable water-repellency to fibrous materials and in particular to textiles, said novel compositions comprising a thermosetting resin binder and an oxazoline of the formula:

R R(;J?Hz N /0 o-x RI wherein R and R are defined as above.

It is a further object of the present invention to provide a process for rendering fibrous materials, and in particular textiles, durably water-repellent by treating the fibrous material with a composition comprising a thermosetting resin binder and an oxazoline of the formula:

R-(|J(|7Hz N 0 CX I l! wherein R and R are defined as above.

Examples of such oxazolines include 2-dodecyl-4-hydroxymethyl-4-ethyl-2-oxazoline, 2-tridecyl-4,4-dimethyl- 2-oxaz0line, 2-pentadecyl-4,4-bis(hydroxymethyl)-2-oxazoline, 2-heptadecyl-4,4-bis(stearoyloxymethyl)-2-oxazoline, 2 (1 hexadecyletheneyl) 4,4 bis(stearoyloxymethyl)-2-oxazoline, Z-hexyl-4,4-dimethyl-2-oxazoline, 2- (1 eicosyletheneyl)-4,4-bis(hydroxymethyl)-2-oxazoline, 2-heneicosyl 4,4 bis(behenoyloxymethyl)-2-oxazoline, and the like. Many of the oxazolines used in the present invention are commercially available. Methods for making oxazolines used in the present invention are disclosed in U.S. Patent 2,504,951, U.S. Patent 2,372,409, U.S. Patent 2,372,410, and patent application Ser. No. 254,010 filed Jan. 25, 1963, for H. L. Wehrmeister and H. I. Yalowitz.

Any suitable thermosetting resin binder which is capable of binding the oxazoline to the fibrous material and compatible with the oxazoline may be utilized in the present invention. Such thermosetting resin binders are well known and many are commercially available. Examples of thermosetting 'resin binders which may be utilized include nitrogen-containing compounds having more than one reactive methylol group such as the ureaformaldehyde condensation products, for example dimethylol ethylene urea, dimethylol urea, dimethylol-1,3-propylene urea, dimethylol-1,3-butylene urea, dimethylol-dihydroxy ethylene urea; the triazones such as 1,3-bis(hydroxymethyl) tetrahydro-S-ethyl-2-triazone, 1,3-bis(hydroxymethyl) -tetrahydro-S-propyl-Z-triazone, 1,3 -bis (hydroxymethyl)-5,5-dimethyl-2-triaz0ne; the pyrimidinones, such as 1,3 bis(hydroxymethyl) tetrahydro-2-pyrimidinone, 1,3 bis(hydroxymethyl) tetrahydro-S-methyl-Z-pyrimidinone, 1,3-bis (hydroxymethyl -tetrahydro-5-hydroxy-2- pyrimidinone, 1,3-bis ('hydroxymethyl -tetrahydro-5-ethyl- Z-pyrimidinone, the melamine formaldehyde condensation products, for example dimethylol melamine, trimethylol melamine, hexamethylol melamine, and the like. Further types of thermosetting resin binders are those having more than one functional aziridinyl group, for example, tris(aziridinyl)phosphine oxide, tris(aziridinyl) phosphine sulfide, carbonyl bisaziridine, N,N-bis(ethyleneiminoformyl)ethylene diamine, N,N-bis(ethyleneiminoformyl)butylene diamine and the like. Additional types of thermosetting resin binders are the dialdehydes and the polymeric acetals. Such dialdehydes include adipaldehyde, succinaldehyde, glutaraldehyde and glyoxal. Such polymeric acetals are those prepared by the condensation of aldehydes such as formaldehyde, propanal, but'anal, etc. with alkylene glycols such as ethylene glycol, diethylene glycol, triethylene glycol, etc. A method for making such acetals is given in US. Patent 2,786,081 to Bernard H. Crest. Still further types of thermosetting resin binders are the epoxides having more than one functional group, for example, 1,3-diglycidyl, glycerol, the diglycidyl ether of ethylene glycol, the diglycidyl ether of 2,2-bis(p-hydroxyphenyl)propane, vinyl cyclohexene diovide, butadiene diepoxide and the like. Mixtures of the foregoing thermosetting resin binders may also be utilized. The weight ratio of oxazoline and thermosetting binder used in the present invention generally should range from about :1 to 1:10. Ratios of oxazoline and thermosetting resin binder of about 5 :1 to about 1:5 are preferred.

The compositions of the present invention can be applied from any suitable form of liquid application medium such as from aqueous emulsions or from solutions in organic solvents such as for example, isopropanol. Suitable application media can be prepared by melting together the two ingredients, that is, the oxazoline and the thermosetting resin binder, and then dispersing the resulting material in the liquid medium. Such hot melts can be formed into emulsions by simply mixing With water and a suitable emulsifier.

When emulsions of the water-repellent compositions of the present invention are to be formed an emulsifying agent should be included. Emulsifying agents are well known to this art and any emulsifying agent ordinarily incorporated in fiber finishing compositions can be employed.

Examples of suitable emulsifiers are the phenoxy polyoxyethylene alcohols, such as alkyl oxyethers and esters and thioethers and esters, having the following general formula: R -A(CH CH O) -CH CH OH, wherein R is a straight or branched chain saturated or unsaturated hydrocarbon group having from about 8 to about 18 carbon atoms or an arylalkyl group having a straight or branched chain saturated or unsaturated hydrocarbon group of from about 8 to about 18 carbon atoms attached to the aryl nucleus and attached to A through the aryl nucleus. A is selected from the group consisting of ethereal oxygen and sulphur, carboxylic esters and thiocarboxylic ester groups and x is a number from 8 to 20. R for example, can be a straight or branched chain octyl, nonyl, decyl, lauryl, myristyl, cetyl or stearyl group or an alkylaryl group such as octyl phenyl, nonyl phenyl, stearyl phenyl, etc. Further types of emulsifying agents are the ethoxylated alkyl phenols and thiophenols having the following general formula:

where R is a straight or branched chain saturated or unsaturated hydrocarbon group having 8 to 18 carbon atoms, B is oxygen or sulphur and x is a number from 8 to 20. R can, for example, be a straight or branched chain octyl, nonyl, decyl, lauryl, cetyl, myristyl or stearyl group. Typical are the condensation products of octyl and nonyl phenol with from 8 to 17 moles of ethylene oxide available under the trade names NIW, Antarox A-400, Igepal CA, and Tergitol NPX. Additional classes of emulsifiers are the polyoxypropylene polyoxyethylene condensates described in US. Patent Nos. 2,674,619 and 2,677,700. Still further types of emulsifiers are the :aliphatic fatty acid partial esters of hexitols, such as sorbital and mannitol and their anhydrides. Typical of this class are sorbitan monooleate, sorbitan mQ Q EQ e and sorbitan monopalmitate.

Especially suitable emulsions are obtained when there is included in the application medium, along with an emulsifier, an oxidized polyolefin wax having a molecular weight of not less than about 750 and an acid number of from 2 to about 50. A typical polyolefin wax is sold under the trade name AC Polyethylene 629 by Allied Chemical Corporation. The weight ratio of oxidized polyolefin wax and oxazoline typically is in the range of from about 10:1 to about 1:10. A preferred weight ratio of oxidized polyolefin wax and oxazoline is in the range of from about 2:1 to about 1:2.

Although the fundamental ingredients of the compositions of the present invention are oxazoline and thermosetting resin binder, numerous other materials may be added to the application medium. The application medium may contain such additives as curing catalysts, softening agents, oil-repellent agents, dyes, pigments, textile lubricants, moth-proofing agents, flame-proofing agents, shrinkproofing agents, brightening agents, sizes, paper-making chemicals such as wet-strength resins, mildew-proofing agents, leather-treating agents, and the like. Material in these groups are well known to those skilled in the art and would be applied to obtain the special effect indicated by the function of the agent. Alternatively, such materials can be applied to the fibrous base material either before or after application of the water-repellent composition.

An advantage of the present invention is that both water repellency and oil repellency can be obtained by application of the composition of the present invention with known per-fluorocarbon oil repellent agents. It is a surprising discovery, however, that oxazolines used in the composition of the present invention enhance the oil repelling ability of the perfluorocarbons and thus serve as extenders for the perfiuorocarbon in providing improved oil repellency. This discovery is of particular advantage because of the high cost of perfluorocarbon oil repellent compositions. By the term extenders, it is meant certain compositions which permit the perfluorocarbons to be used at very low concentrations and still produce desirable oil repellency. Examples of perfluorocarbons suitable for use as oil repellents are perfluorocarbon acid Werner complexes such as those disclosed in US. Patent 2,662,835 and perfluoroacrylate polymers of the general formula:

Typical perfiuoroacrylate polymers are commercially available and are sold under the trade names of Scotchgard and Zepel." The Weight ratio of perfluorocarbon and oxazoline typically is in the range of from about 10:1 to about 1:10 with a preferred range being 2:1 to about 1:2.

When non-durable oil-repellency is suitable the thermosetting resin binder may be omitted from the combination of oxazoline and perfluorocarbon. However, as in most instances when durable oil and water repellency is desired the thermosetting resin binder is essential.

The compositions of the present invention can be applied to fibrous materials by any suitable procedure. Conventional impregnating, padding and like treating apparatus can be employed. Usually, it is convenient to apply the compositions of the present invention by dipping, padding, or immersing. Brushing, spraying, roller coating, electrostatic coating, doctor-blade coating and like procedures can also be employed. Following application of the compositions of the present invention, the base material is preferably dried to remove suspending liquids, and then should be subjected to heat treatment in order to set the thermosetting resin binder on the fibrous base. The temperature employed will depend upon the heat sensitivity of the base and upon the temperature required to aflfect such setting. Typically, temperatures within the range of from about to about 450 F. are utilized. The time required is roughly inversely proportional to the tem- It is apparent from the data that all of the water repellent finishes obtained are durable.

EXAMPLE 1 1 A paper coating bath was prepared containing 3 parts of oxazoline emulsion (the oxazoline was 2-heptadecyl-4- stearoyloxymethyl-4hydroxymethyl-2-oxazoline), 3 parts tris(aziridinyl)phosphine oxide, 1 part ammonium chloride and 93 parts isopropanol.

Pieces of paper were sprayed with the bath and the paper was air dried for 10 minutes at 250 F. The pieces of paper were water repellent.

EXAMPLE 12 A hot melt blend was prepared by heating at 105 C. a mixture containing 30 parts 2-heptaclecyl-4,4-bis(stearoyloxymethyl)-2-oxazoline, 30 parts AC Polyethylene 629 and 15 parts of nonyl phenol-ethylene oxide condensation product. The melt was allowed to cool to 95 C. and to the melt were then added 3 parts of a 20% aqueous solution of potassium hydroxide. To the melt were then slowly added 221 /2 parts of water with accompanying agitation. A homogeneous emulsion was obtained.

A padding bath was prepared by adding 10 parts of the above prepared emulsion to a dispersion of 3 parts of the perfluoroacrylate polymer resin referred to in Examples 3-6 and 87 parts of water.

The padding bath was applied to pieces of cotton sateen cloth. After padding the fabrics were air dried for minutes at 250 F. and cured in an oven for 5 minutes at 300 F.

Oil repellency of the fabric was determined by the oil repellency test referred to above. Samples of sateen cloth treated with a padding bath prepared by dispersing 3 parts of perfluoroacrylate resin latex polymer in 97 parts water and containing no oxazoline were also tested as controls. The results are given in Table IV.

TABLE IV Amount of Amount of Oil Example Number oxazoline perfluoro- Rating Emulsion acrylate (Initial) Control None 3 parts 80 12 parts do 100 wherein R is a radical selected from the group consisting of lower alkyl having from 1 to about 3 carbon atoms, hydroxymethyl, and CH -OOCR R is an alkyl radical having from about 12 to about 22 carbon atoms, R is an alkyl radical having from 1 to about 23 carbon atoms and X is a member selected from the group consisting of H and =CH in the weight ratio of said binder to said oxazoline in the range of 10:1 to 1:10, the

said ingredients being dispersed in a liquid application medium.

2. The composition of claim 1 wherein the liquid medium is an aqueous emulsion.

3. The composition of claim 2 wherein the weight ratio of binder to oxazoline is in the range of about 5:1 to about 1:5.

4. The composition of claim 2 wherein the oxazoline is 2-heptadecyl-4,4-bis(stearoyloxymethyl)-2-oxazoline.

5. The composition of claim 2 wherein the oxazoline is 2-(1-hexadecy1etheneyl)-4,4 bis(stearoyloxymethyl) 2- oxazoline.

6. A composition for imparting water repellency and oil-repellency to fibrous materials which comprises a thermosetting resin binder, a perfluorocarbon selected from the group consisting of perfluorocarbon Werner complexes and perfluoroacrylate polymer resin, and an oxazoline of the formula:

wherein R is a radical selected from the group consisting of lower alkyl having from 1 to about 3 carbon atoms, hydroxymethyl and -CH OOC-R R is an alkyl radical having from about 12 to about 22 carbon atoms, R is an alkyl radical having from 1 to about 23 carbon atoms and X is a member selected from the group consisting of H and =CH in a weight ratio of said binder to said oxazoline of in the range 10:1 to 1:10 and said oxazoline to said perfiuorocarbon of 10:1 to 1:10, the said ingredients 'being dispersed in a liquid medium.

7. The composition of claim 2 wherein the aqueous emulsion contains oxidized polyolefin wax in a weight ratio of said wax to said oxazoline from about 10:1 to about 1:10.

8. A composition comprising an oxazoline of the formula:

wherein R is a radical selected from the group consisting of lower alkyl having from 1 to about 3 carbon atoms, hydroxymethyl and -CH OOCR R' is an alkyl radical having from about 12 to 22 carbon atoms, R is an alkyl radical having from about 1 to 23 carbon atoms and X is a member selected from the group consisting of H and =CH and an oxidized polyolefin wax in the weight ratio of the said oxazoline to the said Wax of about 10:1 to about 1:10.

References Cited UNITED STATES PATENTS 2,905,644- 9/1959 Butter 252-392 3,248,397 4/1966 Purcell 260-307 MORRIS LIEBMAN, Primary Examiner.

HENRY S. KAPLAN, Assistant Examiner.

US. Cl. X.R. 252392; 26029.6

perature and will range from about 5 seconds to about 5 hours. In any case, the temperatures and heating times are so adjusted as to avoid decomposition or damage either to the finish or to the fibrous base.

The compositions of the present invention are applicable to fibrous and particularly textile materials of all types, such as naturally-occurring fibers and blends thereof, for example wool, cotton, silk, cellulose, wood, leather and paper and synthetic fibers such as nylon, rayon, polyacrylonitrile and the like.

The invention will be understood more fully by reference to the following specific examples. It is understood that the examples are presented for purposes of illustration only and are not intended as a limitation of the invention. In the following examples all parts are by weight.

EXAMPLE 1 A hot melt blend was prepared by heating at 105 C. a mixture containing 30 parts 2-heptadecyl-4,4-bis(stearoyloxymethyl)-2-oxazoline, 30 parts of AC Polyethylene 629 (an oxidized waxlike polyolefin, molecular weight about 2000, emulsifiable grade, acid number 114 to 117) manufactured by Allied Chemical Company and 15 parts of nonyl phenol-ethylene oxide condensation product. The melt was allowed to cool to 95 C. and to the melt were added 3 /2 parts of a 20% aqueous solution of potassium hydroxide. To the melt were then slowly added 221 /2 parts of water with accompanying agitation. A homogeneous emulsion was obtained.

A textile padding bath was obtained by mixing 10 parts of this emulsion into a solution of 5 parts trismethoxymethyl melamine, part zinc nitrate and 84 parts water. Pieces of cotton sateen cloth were padded with this bath and air dried for 5 minutes at 250 F. and cured for 5 minutes in an oven at 300 F. The resulting pieces of fabric were Water repellent.

EXAMPLE 2 A padding bath was prepared following the procedure of Example 1 but substituting 2-(l-hexadecyletheneyl) 4,4-bis(stearoyloxymethyl)-2-oxazoline for Z-heptadecyl- 4,4-bis(stearoyloxymethyl)-2-oxazoline. Pieces of cotton sateen fabric were padded with this bath and were dried for 5 minutes at 250 F. and cured in an oven at 300 F. The resulting pieces of fabric were water-repellent.

The fabrics obtained from Examples 1 and 2 were tested for water repellency by American Association of Textile Chemists and Colorists (AAT CC), Test 22-1952. Samples of the fabric were laundered in an automatic type home washer before testing. Other samples were dry cleaned with perchlorethylene before testing. Samples of untreated cotton sateen fabrics were also tested and served as a control. The results of the test on the fabrics are given in Table I.

TABLE I Spray Rating Example Number Initial Washed Dry leaned The above test shows the effectiveness of compositions of the present invention in imparting a durable waterrepellent finish to textiles.

EXAMPLES 36 Four padding baths containing oxazoline and thermo setting resin binder were prepared. The basic formulation was 10 parts of oxazoline emulsion, parts trismethoxymethyl melamine, part 2-amino-2-methyl-l-propanol hydrochloride, part zinc nitrate and 83 /2 parts water. The oxazoline emulsion was prepared as set forth in Example 1. To each two of the padding baths were added three parts of a perfiuoroacrylate polymer latex (30% solids) having the following general formula:

where RF-- is a fiuorinated alkyl group.

These padding baths were then applied to pieces of cotton sateen cloth. After padding the fabrics were air dried for 5 minutes at 250 F. and cured in an oven for 5 minutes at 300 F.

Water repellency of the fabrics was determined by AATCC Test 22-1952. Oil repellency of the fabrics treated with the padding baths containing the perfiuoroacrylate resins was determined in accordance with the test described in Minnesota Mining and Manufacturing Company, Textile Chemical Bulletin, Appendix A, January 1962, page 1, and referred to as 3M Oil Repellency Test. The test is based on the different penetrating properties of two hydrocarbon liquids, namely, mineral oil and n-heptane. The mineral oil and n-heptane proportions for each rating were selected to give oil stain resistance ratings comparable to spray ratings of AATCC Test 22- 1952. Samples of cotton sateen cloth treated with a padding bath of the basic composition containing 3 parts of perfiuoroacrylate resin but containing no oxazoline were also tested as control. The results are given in Table II.

TABLE II Amount of Water Oil perfiuoro- Spray Rating aerylate Rating parts 0 None Example Number Oxazoline 4,4-bis(behouoyloxymethyl)-2-oxazoline. 6 do 3 parts It is apparent that both water repellency and oil repellency are obtained with padding baths containing oxazoline, thermosetting resin binder and perfiuorocarbon. It is also apparent that better oil repellency is obtained with padding baths containing oxazoline, thermosetting resin binder and perfluorocarbon than is obtained with padding baths from which the oxazoline has been omitted.

EXAMPLES 7-10 Four padding baths containing oxazoline, thermosetting resin binder and perfiuoroacrylate resin were prepared. The basic formulation was 10 parts oxazoline emulsion, 5 parts trismethoxymethyl melamine, part 2-amino-2- methyl-l-propanol hydrochloride, /1 part zinc nitrate, 83 /3 parts water and 3 parts perfiuoroacrylate latex. The oxazoline emulsion Was prepared as set forth in Example 1. These padding baths were applied to pieces of cotton sateen cloth. After padding the fabrics were air dried for 5 minutes at 250 F. and cured in an oven for 5 minutes at 300 F.

Water repellency and oil repellency of the fabrics were determined as in Examples 3-6. The results of the test are given in Table III.

methyl) -2-oxazoline. 

